A conjugated, pyridine‐containing, phenylethynyl ligand that forms complexes with AgI and PdII has been developed. NMR titration studies with PdII reveal a stoichiometric binding of the ligand to the metal atom, while similar studies with AgI reveal a binding that is dynamic on the NMR timescale. Analysis of the NMR spectroscopic data by Job's plot analysis and non‐linear curve fitting of a titration curve reveals a 1:1 binding ratio of ligand/silver cation and an association constant of Ka = 53 M–1. X‐ray crystal structures of the ligand–metal complexes suggest ample room for the nearly barrierless rotation of the unsubstituted central benzene ring of the para‐phenylethynyl chain. Subtle electronic differences in substituted systems provide some evidence of impaired rotation. Conjugated ligands: A trans‐spanning ligand that binds AgI and PdII has been developed and studied by X‐ray crystallography and 1H NMR spectroscopy. UV/Vis spectroscopy was used to investigate what effect metal binding might have on the conjugation in the para‐phenyleneethynylene backbone.